US20140069302A1 - Use of precipitated carbonate in the manufacture of a fibre product - Google Patents

Use of precipitated carbonate in the manufacture of a fibre product Download PDF

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US20140069302A1
US20140069302A1 US13/823,050 US201213823050A US2014069302A1 US 20140069302 A1 US20140069302 A1 US 20140069302A1 US 201213823050 A US201213823050 A US 201213823050A US 2014069302 A1 US2014069302 A1 US 2014069302A1
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filler
carbonate
fibre
pulp
mixture
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Sakari Saastamoinen
Teemu Grönblom
Lars Grönroos
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Nordkalk Oy AB
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Nordkalk Oy AB
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C04B14/28—Carbonates of calcium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C09C1/022—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/028—Compounds containing only magnesium as metal
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to a filler or a filler mixture, which contains carbonate, and to a process for the manufacture thereof by precipitating the filler directly into the pulp or as a separate process without the presence of fibres, particularly from the white water of the paper or board manufacture.
  • the invention also relates to a fibre product which contains said filler, such as a paper or board product, or a plastic, rubber, concrete or paint product.
  • precipitated calcium carbonate has been growing strongly particularly in the paper and board manufacture, the processing of rubbers and plastics, and the manufacture of printing inks, paints, and adhesives.
  • Precipitated calcium carbonates have an excellent brightness and scattering ability, as well as a low price.
  • precipitated calcium carbonate can increase the mechanical strength, when used in the applications mentioned above.
  • These calcium carbonates have a crystal structure that typically is in the form of calcite, aragonite, or vaterite.
  • Calcite is typically found in crystal forms, such as the scalenohedral, rhombohedral, cubic, and prismatic forms.
  • Aragonite is orthorhombic and it is typically found in elongated forms.
  • vaterite is unstable, changing into calcite and aragonite.
  • vaterite has a spherical shape. The crystal form can be transformed into acicular, cubic, spherical, and many other crystal forms by changing the reaction conditions, such as the concentration of the slaked lime and the reaction temperature.
  • the strength of paper and board mainly develops between the fibre and the charged groups of fines, due to hydrogen bonds. These charged groups particularly include hydroxyl and carboxyl groups.
  • When improving the strength it is primarily done in a mechanical manner by grinding the fibres, thereby attempting to increase the fibrillation of the fibres.
  • the strength is dependent on the strength of an individual fibre grade, the strength between the fibres, the number of fibre bonds, as well as the distribution of fibres and bonds in the finished paper or board.
  • the fillers or pigments that are used in the manufacture of paper and board have an average particle size of less than 5 ⁇ m, and they have a light colour.
  • the most typical fillers include kaolins, talcs, ground calcium carbonate (GCC), and precipitated calcium carbonate (PCC).
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • precipitated aluminium silicates satin white
  • titanium dioxide precipitated aluminium silicates
  • Drawing an exact line between fillers and coating pigments is difficult, but roughly fillers have a larger size and a coarser shape than the pigments used in coating.
  • an optimal particle size for the most common fillers and coating pigments, from the point of view of maximum light scattering is about 0.4-0.5 ⁇ m.
  • the average particle size of coating pigments is, however, 0.5-1 ⁇ m, and that of fillers 1.5-4 ⁇ m.
  • fillers and pigments are used as well as other fillers.
  • calcium carbonates both the ground (GCC) and precipitated (PCC) forms, are widely used because of their low price and good light scattering properties, particularly in replacing the fibre of chemical pulp. Paper and board that is manufactured from recycled, de-inked and mechanical pulps could be replaced with calcium carbonates, but the darkening of mechanical pulp caused by alkali often limits their use in the manufacture of the paper and board grades manufactured from these pulps.
  • the decrease in strength and stiffness of the paper or board product when the fibre is replaced with filler are mainly caused by the fillers weakening the generation of hydrogen bonds between the fibres, since the surface of the fillers does not form hydrogen bonds.
  • the filler is generally added directly to the pulp. In the wire section, only a portion of the added filler is attached to the finished paper or board web. Regardless of this, the rest of the filler is conducted through the white water system to form a part of the finished paper or board structure, but then the risks of various runnability problems have increased mainly due to the attachment of various hydrophobic substances to the fillers of the white water system.
  • An object of the present invention is to provide a new fibre product, such as a paper or board product, which has a high strength, brightness, ink density, and opacity.
  • Such a carbonate-containing filler and fibre product can be provided, for example, by the process according to the invention.
  • the present invention thus relates to the carbonate-containing filler and to the production process of the same.
  • a filler is further utilised in the process of manufacturing the fibre product according to the invention, wherein the fibre product contains chemical pulp fibre and/or wood fibre and/or synthetic fibre, and which preferably is paper or board.
  • carbonate filler is attached between the chemical pulp fibres or wood fibres and to the fibrils, whereafter said fibre product is produced from the pulp.
  • the process of manufacturing the carbonate-containing filler comprises forming an acidic bicarbonate ion solution from a corresponding hydroxide solution by adding carbon dioxide to the solution, and forming a carbonate portion of the filler by increasing the pH of the obtained acidic bicarbonate ion solution to a neutral or alkaline range by means of underpressure or centrifugal force or a combination thereof.
  • the carbonate-containing filler or filler mixture according to the invention comprises at least its carbonate portion manufactured by a process comprising forming a carbonate portion of the filler by increasing the pH of the obtained acidic bicarbonate ion solution to a neutral or alkaline range by means of underpressure or centrifugal force or a combination thereof.
  • the process of manufacturing the fibre product is such that wherein at least the carbonate portion of the used filler is formed in an aqueous solution used for the manufacture of the pulp, before the pulp is compressed into the fibre product, or it is formed in a coating mix before the optional coating of the fibre product, and the filler is used in plastic, concrete, rubber or paint.
  • Particularly advantageous properties are achieved when a polymer that increases the dry strength is used together with the carbonate in the filler or with the filler in the manufacture of the fibre product.
  • FIG. 1 is a graphic depiction of the impact of the particle size of the carbonate filler (APS) and a portion of starch on the TEA values (TEA1) of the fibre product, when a basis weight of 80 g/m 2 and 10% of carbonate filler are used in the fibre network.
  • APS carbonate filler
  • TEA1 TEA1
  • FIG. 2 is a graphic depiction of the impact of the particle size of the carbonate filler (APS) and a portion of starch on the Scott Bond values (Scottl) of the fibre product, when a basis weight of 80 g/m 2 and 10% of carbonate filler are used in the fibre network.
  • APS carbonate filler
  • Scottl Scott Bond values
  • FIG. 3 is a graphic depiction of the brightness and opacity values of kaolins and the carbonate filler (a size category of 6.5 ⁇ m). The results are normalized to a filler content of 6% in a basis weight of 80 g/m 2 .
  • FIG. 4 shows scanning electron microscope images of chemical pulp sheets of 80 g/m 2 , comprising carbonate fillers of a size category of 13 ⁇ m (the upper row) and 6.5 ⁇ m (the lower row) on the surface of the sheets.
  • the precipitated calcium carbonate is manufactured by changing the pH from alkaline toward neutral.
  • the pH is increased from acidic to a pH of over 7.
  • the purpose is to provide carbonate at the precipitation stage, which together with possible polymers increasing the dry strength could increase the strength of the filler-containing network in the final product, without weakening the optical properties (opacity and brightness).
  • the present invention thus relates to a process of manufacturing a filler containing carbonate, wherein an acidic bicarbonate ion solution is formed from a corresponding hydroxide solution by adding carbon dioxide to said hydroxide solution, whereafter the carbonate portion of the filler is formed by increasing the pH of the formed acidic bicarbonate ion solution to a neutral or alkaline range by means of underpressure or centrifugal force or a combination thereof.
  • Acidic in this context refers to a pH value of below 7, whereas “neutral” refers to a pH value within 7-8, and “alkaline” refers to a pH value of over 8, particularly over 10.
  • Underpressure or negative pressure in this context refers to a pressure under ambient pressure or air pressure, preferably within the range of 0.60-1 bar, i.e. as an absolute pressure 0.4-0 bar; more preferably within the range of 0.85-0.95 bar, i.e. as an absolute pressure 0.15-0.05 bar; particularly within the range of 0.88-0.94 bar, i.e. as an absolute pressure 0.12-0.06 bar.
  • a speed of rotation of 50-2000 rpm (rotations per minute) is preferably used.
  • the temperature while carrying out the stages of the process can be close to ambient temperature (about 25° C.) or slightly higher, particularly 35-70 ° C.
  • the used hydroxide is preferably calcium hydroxide or magnesium hydroxide or a mixture thereof. More preferably the used hydroxide is manufactured by elutriating burnt lime, burnt dolomite, MgO or another source of calcium or magnesium in water or an aqueous solution, which when elutriated in such a solution gives an alkaline solution, or by elutriating a mixture of two or more of the above.
  • the hydroxide and the carbon dioxide can be added to said aqueous solution essentially at the same time. Optionally, they are added at different stages.
  • aqueous solution refers to all solutions or suspensions which contain more than 50% by weight of water. Consequently, the aqueous solutions include both pure water (100% by weight of water) and dilute fibre suspensions.
  • any of the aqueous solutions of the paper or board machine can be converted into the bicarbonate ion solution suitable for use as the starting material solution of the process.
  • said aqueous solution is a process water of the paper or board manufacture, particularly circulation water.
  • soluble carbon dioxide (CO 2 ) and, to a minor extent, carbonic acid (H 2 CO 3 ), are the main states of carbonate.
  • bicarbonate or hydrogen carbonate (HCO 3 ⁇ ) is the main state of carbonate up to a pH of about 10.
  • carbonate (CO 3 2 ⁇ ) is the main state.
  • the alkalinity of carbonate refers to the content of strong acid, with which the aqueous solution can be titrated to the end point of phenolphthalein. At this point, all of the CO 3 2 ⁇ has been converted into the ion state HCO 3 ⁇ . This takes place at a pH of about 8.3. In the most important pH range of the paper and board manufacture, pH 6-8, bicarbonate (HCO 3 ⁇ ) is the predominant state. Further, reasonably well dissolved carbon dioxide and some carbonic acid and colloidal carbonate have entered this pH range from the acidic side of the pH range.
  • the solution in the acidic pH range (pH ⁇ 7) is herein called the acidic bicarbonate ion solution.
  • This acidic solution thus has a pH value of ⁇ 7, preferably ⁇ 6.7, and most suitably ⁇ 6.5, among others, to avoid early precipitation of the carbonate.
  • carbonate is formed from the bicarbonate ions in the solution. It is common knowledge that bicarbonate ions can be precipitated into carbonate particles from a carbonate ion solution by increasing the pH or the temperature.
  • the carbonate particles can be precipitated according to the following reaction equations:
  • the present invention is based on a situation where sufficiently warm bicarbonate ion solution (of at least room temperature) is subjected to underpressure or the effect of centrifugal force, so that carbon dioxide is released to the air from the solution.
  • calcium carbonate is commonly used as the carbonate, both as a filler and as a coating pigment.
  • Well-known forms of calcium carbonate include ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC).
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • GCC ground calcium carbonate
  • the aim has been to keep their average particle size as larger than 500 nm, typically 1-2 ⁇ m, as it is believed that the best possible light scattering efficiency (brightness and opacity) is then achieved.
  • Their solubility in water is fairly low under normal conditions. However, under acidic conditions soluble calcium ions are released, increasing the hardness of the water.
  • the average particle size (APS50) of the carbonate manufactured according to the present invention is preferably 0.5-15 ⁇ m, particularly 1-8 ⁇ m.
  • Further filler can be added to the acidic bicarbonate ion solution used in the invention before the carbonate portion of the filler is formed from the solution.
  • This added filler is preferably commercial GCC or PCC or a mixture thereof or, optionally, a filler other than carbonate, such as wollastonite, aluminium silicate, kaolin, talc, satin white or a titanium oxide.
  • carbonate portion in this context refers to the solid carbonate of the filler or filler mixture which is to be formed or is formed online, thus describing the carbonate content in comparison with the added fillers or corresponding additives. This portion is preferably >5%.
  • a dry strength polymer is used with the carbonate portion of the filler, preferably being selected from the group of starch, aldehyde starch, guar gum, polyacrylamide, glyoxilized polyacrylamide, carboxyl methyl cellulose, polyvinyl alcohol, latex or citosane, or a mixture of two or more of the above, most preferably from a starch.
  • fillers In the paper or board industry, the decrease in dry strength caused by the use of fillers has typically been compensated using water-soluble natural and artificial polymers.
  • the use of fillers increases the need to use dry strength agents.
  • the most typical dry strength agents include starch, carboxyl methyl cellulose (CMC), guar gum, and polyacrylamide (PAM).
  • CMC carboxyl methyl cellulose
  • PAM polyacrylamide
  • Polyvinyl alcohol and latex can also be used as dry strength polymers, even though in practice, they are generally not used in the wet section of the paper or board manufacturing process.
  • Starch is the oldest and most commonly used dry strength agent in increasing the strength of fibre networks, its strength-increasing impact being caused by its large amount of hydroxyl groups, which increase the generation of hydrogen bonds.
  • Cationic and amphoteric starches are the most commonly used starches. Generally, when these are added to high consistency pulp, the effect is primarily an increase in the strength properties.
  • an ether bond can be formed in the starch in the manufacture of carboxyl methyl cellulose (CMC).
  • Native starch can further be esterified, oxidized, hydrolyzed, and treated using a combination of enzymes and heating or some or all of the above.
  • the most typical sources of native starch are potato, barley, wheat, corn and tapioca. However, when added to a dilute pulp or short circulation pulp, the starch improves the retention of the fines and filler, instead of increasing the strength.
  • starch is used in the dispersion of stock sizes, such as AKD and ASA.
  • the surface sizing of paper is also often carried out with starch, as well as the attachment of the various layers of board to each other.
  • the carbonate filler is manufactured so that the aqueous solution is first rendered acidic by dosing carbon dioxide into it either simultaneously or before burnt lime or dolomite or the corresponding hydroxide solutions thereof is/are added to the aqueous solution.
  • the bicarbonate ion solution according to the invention which has been acidified, is then obtained.
  • the pH of the solution is increased to the neutral or alkaline range by under-pressurisation, whereby the carbonate filler according to the invention is generated.
  • the present invention also relates to the filler or filler mixture containing carbonate which has been manufactured by means of the above-described process.
  • the filler or filler mixture in question is thus manufactured by a process, wherein the pH is increased by means of underpressure or centrifugal force or a combination thereof from the acidic range to the neutral or alkaline region.
  • This filler contains at least 5% by weight, preferably 25-100% by weight, most suitably 50-90% by weight of carbonate, which has been formed in solid form in the aqueous solution.
  • the average particle size of this carbonate is preferably 0.5-15 ⁇ m, particularly 1-8 ⁇ m.
  • the carbonate is preferably selected from calcium or magnesium carbonate or a mixture thereof. Most suitably, the filler consists of this calcium or magnesium carbonate or a mixture thereof.
  • Particularly preferred fillers in the connection of the invention are ground calcium carbonate (GCC), precipitated calcium carbonate (PCC) or mixtures thereof.
  • the pH of the filler formed according to the invention is neutral or alkaline.
  • the final pH value of the filler is preferably 6-8.
  • the carbonate manufactured online, according to the invention, can also be mixed with the additional filler into a filler mixture.
  • This added filler is preferably commercial GCC or PCC or a mixture thereof, or, optionally, it contains a filler other than a carbonate, such as wollastonite, aluminium silicate, kaolin, talc, satin white or a titanium oxide.
  • the carbonate portion of the filler is in the final filler already mixed with the dry strength polymer, most preferably in the pulp, which polymer preferably is selected from the group of starch, aldehyde starch, guar gum, polyacrylamide, glyoxilized polyacrylamide, carboxy-methyl cellulose, polyvinyl alcohol, latex or citosane, or a mixture of two or more of the above, most preferably from a starch.
  • the present invention further relates to a process of manufacturing a fibre product containing chemical pulp fibre, wood fibre or synthetic fibre, or a mixture thereof.
  • the pulp is manufactured, to which the carbonate-containing filler is added, whereafter the pulp is compressed into a fibre product, which optionally is coated.
  • the used filler or filler mixture increases the optical properties of the structure of the fibre product to be manufactured, and maintains its strength properties, optionally together with the water-soluble, dry strength -increasing polymer.
  • the fibre product refers to a thin, plate-like fibre product, which particularly is a paper or board product.
  • the fibres of the product can be any natural fibres or synthetic fibres or a mixture thereof.
  • the fibres can be chemical pulp or mechanical pulp or a mixture thereof.
  • sulphate and sulphite cellulose fibres dissolving pulp, nanocellulose, chemi-mechanical (CTMP), thermomechanical pressure groundwood (TMP), pressure groundwood (PGW), groundwood pulp, recycled fibre, or fibres of de-inked pulp can constitute the fibres of the product.
  • CMP chemi-mechanical
  • TMP thermomechanical pressure groundwood
  • PGW pressure groundwood pulp
  • recycled fibre or fibres of de-inked pulp
  • fibres of de-inked pulp can constitute the fibres of the product.
  • sulphate and sulphite celluloses are called chemical pulps
  • thermo-mechanical pulp, pressure groundwood, and groundwood pulp are called mechanical pulps.
  • the consistency of pulp made from these fibres, when the filler or filler mixture according to the invention is added thereto, is preferably 0.1-5%, particularly 0.2-1.
  • a “filler” specifically refers to the particles, which are added or attached to the gaps between the fibres, and the purpose of which is to reduce the fibre content of the final product.
  • the definition also covers pigments, including coating pigments.
  • such known fillers and pigments of the paper and board manufacture have an average particle size of less than 5 ⁇ m, and they have a light colour.
  • the most typical fillers include kaolins, talcs, ground calcium carbonate (GCC), and precipitated calcium carbonate (PCC).
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • precipitated aluminium silicates satin white
  • titanium dioxide precipitated aluminium silicates
  • Drawing an exact line between fillers and coating pigments is difficult, but roughly, fillers have a larger size and a coarser shape than the pigments used in coating.
  • an optimal particle size for the most common fillers and coating pigments, from the point of view of maximum light scattering is about 0.4-0.5 ⁇ m.
  • the average particle size of coating pigments is, however, 0.5-1 ⁇ m, and that of fillers 1.5-4 ⁇ m.
  • the carbonate portion of the filler used in the fibre product is formed in the aqueous solution to be used in the manufacture of the pulp before the pulp is compressed into the fibre product, or it is formed in a coating paste before the optional coating of the fibre product.
  • the aqueous solution, in which the carbonate portion is formed is then the process water of the paper or board manufacture, preferably the circulation water, particularly before the head box of the machine.
  • the above-described process is used, wherein the pH is increased from the acidic range to the neutral or alkaline range by means of under-pressure or centrifugal force or a combination thereof.
  • the carbonate to be formed is preferably calcium or magnesium carbonate or a mixture thereof.
  • a dry strength polymer is used in the pulp with the carbonate portion of the filler, preferably selected from the group of starch, aldehyde starch, guar gum, polyacrylamide, glyoxilized polyacrylamide, carboxyl methyl cellulose, polyvinyl alcohol, latex or citosane, or a mixture of two or more of the above, most suitably from a starch.
  • the amount of optionally used starch is 0-40 kg/t of pulp. Increasing the addition from this limit weakens among others the dewatering of the wire section. This is caused by the anionic charge of the fibres and the filler being neutralized by the cationic starch, whereby the rest of the starch no longer attaches to the fibres and the filler, but remains in the form of dissolved starch in the circulation waters.
  • the structure of the fibre product manufactured according to the invention would improve the opacity and printability of the product, when the carbonate filler that is brighter than the fibres is incorporated into the fibre network. This improves the light scattering and the absorption of ink.
  • the increase in strength properties with the same filler and filler content is due to the carbonate filler still being in an unstable, amorphous state when brought together with the fibres, whereby the carbonate filler is capable of increasing the strength bonds between the hydroxyl groups of the dry strength polymer and the hydrogen-bonding groups of the fibre.
  • the acidic bicarbonate ion solution was manufactured by mixing 100 or 200 g of burnt lime (CaO) with 500 g or 1000 g, respectively, of water at 45° C.
  • the Ca(OH) 2 slurry thus generated was added to 30 litres of tap water.
  • the water and the calcium hydroxide were allowed to react with carbon dioxide conveyed to the mixture, so that the pH of the mixture at the end of the reaction was 6.3.
  • the precipitate that sedimented on the bottom was separated from the dissolved and colloidal material (Ca ions, carbonic acid, bicarbonate and colloidal calcium carbonate).
  • the precipitate that sedimented on the bottom was not used in the tests.
  • the bicarbonate ion solution thus manufactured was used as raw material in the precipitation tests described below.
  • the 100 g of CaO in 30 litres contained 5.6 g/l of carbonate after the underpressurisation.
  • the 200 g of CaO in 30 litres contained 11.3 g/l of carbonate after the underpressurisation.
  • the bicarbonate ion solutions (30 litres) manufactured according to the previous example were used, 100 g of calcium oxide having been added to one of them and 200 g of calcium oxide to the other. The precipitate that sedimented on the bottom was not used in the tests.
  • the bicarbonate solutions were heated to 55° C., after which an underpressure of 0.92 bar (i.e. an absolute pressure of 0.08 bar) was allowed to influence the bicarbonate ion solution in a 50-litre steel container. The underpressure was created by means of a pump.
  • Tables 2 and 3 show the delay times, after which the samples were taken out of the underpressure container, and the measured properties of the samples.
  • the underpressure conditions used for the particle size were selected according to the previous Example 2.
  • the delay time of the underpressure is used to influence the particle size (APS) of the carbonate filler.
  • 0 micrometers means that no carbonate filler is manufactured in the pulp.
  • the carbonate filler sizes of 6.5 and 13 micrometers correspond to the delays of 40 seconds (100 g CaO/30 l), 6.5 ⁇ m and 600 seconds (200 g CaO/30 l), 13 ⁇ m at an underpressure of 0.92 bar and a temperature of 45°, respectively.
  • underpressure a 50-litre steel container was used, in which the underpressure was formed by means of a pump.
  • the cationic pulp starch used in the tests was from Chemigate Oy (Raisamyl, the DS of which was 0.035). Every time when used, the pulp starch was added to the 3.8% pulp at a mixing time of 1 minute before diluting it to a consistency of 0.2%. Kaolins (Capim and Intramax) were added to the 0.2% pulp. The bicarbonate ion solutions manufactured according to Example 1 were used for the dilution of the pulp from 3.8% to 0.2%. The carbonate fillers were manufactured from this by underpressurisation. As a retention agent, 200 g/t of PAM (Fennopol 3400, Kemira) were added to the sheet mould during the mixing.
  • test points of the test plan are presented in Table 4.
  • the index of determination for the final model is over 95%.
  • the strength was measured both as Scott Bond and TEA values.
  • the optical values measured included opacity and brightness (ISO).
  • the strength Scott & TEA
  • FIG. 1 shows that the best TEA strength is achieved, when the particle size of the carbonate filler is about 6.5 micrometers and the amount of pulp starch is 5 kg/t.
  • the corresponding TEA strengths, J/m 2 , achieved at the control points were:
  • Control 1 Control 2 70 Control 3 90.
  • FIG. 2 shows that the starch portion of 10 kg/t and no carbonate filler yields the best Scott Bond strength.
  • the corresponding Scott Bond strengths, J/m 2 , achieved at the control points were:
  • Control 1 214 Control 2 302 Control 3 324.
  • FIG. 4 shows the carbonate particles of each size category, both 6.5 and 13 ⁇ m, on the surface of the manufactured chemical pulp sheets of 80 g/m 2 .
  • the carbonate fillers of 6.5 ⁇ m in the lower row one can also observe porosity in the structure of the carbonate filler.
  • FIG. 4 also shows how the carbonate fillers are clearly bonded to the fibrous substance (starch and/or fibrils of the fibre).
  • the 3.8% pulp was diluted to a consistency of 0.2% with the bicarbonate ion solution and, subsequently, 10% or 20% of either GCC or PCC was added to this diluted pulp, while evenly agitating, before the underpressurisation.
  • GCC and PCC underpressurisations are called GCC and PCC underpressurisations in Table 5, where the results normalized to a filler content of 5% are shown.
  • the bicarbonate ion solution was manufactured according to Example 1 by adding 100 g of calcium oxide to 30 litres of the manufactured solution. The 0.2% fibre pulp and either 10% or 20% of GCC or PCC, diluted with the bicarbonate ion solution used, were conducted to the underpressurisation. Thereafter, this mixture was kept at an underpressure of 0.92 bar for 40 seconds.
  • the basis weights of the sheets were at the target basis weight of 80 g/m 2 , with an accuracy of ⁇ 0.6 g/m 2 .
  • the assessment of the printing properties of the sheets in this test was made by measuring the consistency.
  • the sheets were printed by the Universial Testprinter (Testprint B.V.) by using a Cold set black (Sun Chemical, viscosity 7.3 Pas) with 10 milligrams of ink on the upper surface of the sheet.
  • the consistencies were measured by a densitometer (Macbeth) from the aerated and dried samples after 24 hours from the printing.
  • the Universial testprinter employed a pressure of 630 N and a velocity of 1 m/s.
  • the results are normalized to the same filler content of 5%.
  • Table 6 the results are shown, normalized to a filler content of 5%. 95% means a confidence interval of 95%.

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US9376345B2 (en) 2013-06-25 2016-06-28 Carboncure Technologies Inc. Methods for delivery of carbon dioxide to a flowable concrete mix
US9388072B2 (en) 2013-06-25 2016-07-12 Carboncure Technologies Inc. Methods and compositions for concrete production
US9492945B2 (en) 2012-10-25 2016-11-15 Carboncure Technologies Inc. Carbon dioxide treatment of concrete upstream from product mold
US9580867B2 (en) 2013-04-26 2017-02-28 Pacific Nano Products, Inc. Fibrous structured amorphous silica including precipitated calcium carbonate, compositions of matter made therewith, and methods of use thereof
US9738562B2 (en) 2013-06-25 2017-08-22 Carboncure Technologies Inc. Methods and compositions for concrete production
US9777143B2 (en) 2014-04-11 2017-10-03 Georgia-Pacific Consumer Products Lp Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles
US9777129B2 (en) 2014-04-11 2017-10-03 Georgia-Pacific Consumer Products Lp Fibers with filler
US9790131B2 (en) 2013-02-04 2017-10-17 Carboncure Technologies Inc. System and method of applying carbon dioxide during the production of concrete
US10350787B2 (en) 2014-02-18 2019-07-16 Carboncure Technologies Inc. Carbonation of cement mixes
US10570064B2 (en) 2014-04-07 2020-02-25 Carboncure Technologies Inc. Integrated carbon dioxide capture
US10927042B2 (en) 2013-06-25 2021-02-23 Carboncure Technologies, Inc. Methods and compositions for concrete production
US11660779B2 (en) 2016-04-11 2023-05-30 Carboncure Technologies Inc. Methods and compositions for treatment of concrete wash water
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CN108676386B (zh) * 2018-05-04 2020-11-10 内蒙古超牌建材科技有限公司 低粘度煅烧高岭土、低粘度煅烧高岭土料浆及其制备方法

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US9492945B2 (en) 2012-10-25 2016-11-15 Carboncure Technologies Inc. Carbon dioxide treatment of concrete upstream from product mold
US9790131B2 (en) 2013-02-04 2017-10-17 Carboncure Technologies Inc. System and method of applying carbon dioxide during the production of concrete
US10683237B2 (en) 2013-02-04 2020-06-16 Carboncure Technologies Inc. System and method of applying carbon dioxide during the production of concrete
US11447641B2 (en) 2013-04-26 2022-09-20 Pacific Nano Products, Inc. Fibrous structured amorphous silica including precipitated calcium carbonate and compositions of matter made therewith
US9580867B2 (en) 2013-04-26 2017-02-28 Pacific Nano Products, Inc. Fibrous structured amorphous silica including precipitated calcium carbonate, compositions of matter made therewith, and methods of use thereof
US9637864B2 (en) 2013-04-26 2017-05-02 Pacific Nano Products, Inc. Fibrous structured amorphous silica including precipitated calcium carbonate, compositions of matter made therewith, and methods of use thereof
US9708770B2 (en) 2013-04-26 2017-07-18 Pacific Nano Products, Inc. Paper, paperboard, or label stock coated with fibrous structured amorphous silica including precipitated calcium carbonate
US10077363B2 (en) 2013-04-26 2018-09-18 Pacific Nano Products, Inc. Fibrous structured amorphous silica including precipitated calcium carbonate and compositions of matter made therewith
US10246379B2 (en) 2013-06-25 2019-04-02 Carboncure Technologies Inc. Methods and compositions for concrete production
US9463580B2 (en) 2013-06-25 2016-10-11 Carboncure Technologies Inc. Methods for carbonation of a cement mix in a mixer
US11773031B2 (en) 2013-06-25 2023-10-03 Carboncure Technologies Inc. Apparatus for delivery of a predetermined amount of solid and gaseous carbon dioxide
US9758437B2 (en) 2013-06-25 2017-09-12 Carboncure Technologies Inc. Apparatus for delivery of carbon dioxide to a concrete mix in a mixer and determining flow rate
US9738562B2 (en) 2013-06-25 2017-08-22 Carboncure Technologies Inc. Methods and compositions for concrete production
US9108883B2 (en) 2013-06-25 2015-08-18 Carboncure Technologies, Inc. Apparatus for carbonation of a cement mix
US11773019B2 (en) 2013-06-25 2023-10-03 Carboncure Technologies Inc. Methods and compositions for concrete production
US9376345B2 (en) 2013-06-25 2016-06-28 Carboncure Technologies Inc. Methods for delivery of carbon dioxide to a flowable concrete mix
US10927042B2 (en) 2013-06-25 2021-02-23 Carboncure Technologies, Inc. Methods and compositions for concrete production
US9388072B2 (en) 2013-06-25 2016-07-12 Carboncure Technologies Inc. Methods and compositions for concrete production
US10350787B2 (en) 2014-02-18 2019-07-16 Carboncure Technologies Inc. Carbonation of cement mixes
US10570064B2 (en) 2014-04-07 2020-02-25 Carboncure Technologies Inc. Integrated carbon dioxide capture
US11878948B2 (en) 2014-04-07 2024-01-23 Carboncure Technologies Inc. Integrated carbon dioxide capture
US9777143B2 (en) 2014-04-11 2017-10-03 Georgia-Pacific Consumer Products Lp Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles
US10696837B2 (en) 2014-04-11 2020-06-30 Gpcp Ip Holdings Llc Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles
US10597501B2 (en) 2014-04-11 2020-03-24 Gpcp Ip Holdings Llc Fibers with filler
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